Insoluble polymeric diazonium salt chromogen

ABSTRACT

A novel insoluble polymeric diazonium salt chromogen consisting of a diazotized aromatic polyamine bound by an amide linkage to a cation exchange resin can be prepared by reacting a cation exchange resin containing carboxylic acid groups or salts of such carboxylic acid groups with a halogenating agent to convert some of the resin carboxylic acid groups or salts of such acid groups to acyl halide groups, reacting the resulting acyl halide groups with an aromatic polyamine to form a resin containing amide linkages and free aromatic amino groups, and then diazotizing the free aromatic amino groups. The resulting insoluble chromogen can be used to detect coupling compounds by forming colored reaction products with such coupling compounds. This chromogen can also be used to detect enzyme activity wherein the enzyme catalyzes a reaction with a suitable substrate to release a coupling compound which will form a colored reaction product with the insoluble chromogen.

United States Patent US. Cl. 252-529 8 Claims ABSTRACT OF THE DISCLOSUREA novel cleaning composition useful for removing grease and/ or carbonfrom stoves, grilles, cooking utensils and the like. The compositioncomprises an aqueous or substantially aqueous mixture of sodiumhydroxide, a dimethyl polysiloxane, tetrasodium pyrophosphate, apolyethylene oxide mono and/or dihydrogen phosphate ester, a nonylphenol polyethylene glycol ether and triethanol amine.

CROSS REFERENCE TO RELATED APPLICATIONS This application is acontinuation-in-part of U .S. patent application Ser. No. 779,618 filedNov. 27, 1968 now abandoned.

BACKGROUND OF THE INVENTION Part I.The field of the invention Thisinvention relates to cleaning compositions. More precisely, theinvention disclosed herein relates to a cleaning composition especiallyuseful for removing accumulated grease or carbon from equipment such asstoves, grilles and related cooking equipment.

Part II.Description of the prior art The problem of removing accumulatedgrease and carbon from grilles or like utensils and from the exteriorand interior of stoves is one which is long outstanding in the art. Thisis particularly true in commercial establishments where the grilles andstoves are continually used throughout the business hours. In suchestablishments, considerable time and eEort is expended in cleaningequipment of the type described. For example, the grilles normallyemployed must be cleaned at least daily. Presently, the celaningoperation involves the use of detergents or soaps usually in combinationwith an abrasive material such as pumice or the like. Depending upon thesize of the grille, the operation will oftentimes consume the betterpart of an hour or more. The cleaning of the exterior or interior ofstoves is equally ineflicient and time consuming since the stove mustoftentimes be cooled before the operation can commence. Accordingly, thegrease becomes more resistant to the cleaning composition employed andexcess time is consumed.

SUMMARY OF THE INVENTION In accordance with the practice of the presentinvention a novel cleaning composition is presented which issurprisingly eifective in rapidly removing accumulated grease and carbonfrom cooking equipment. The composition of the present inventioncomprises a mixture of essential ingredients which include sodiumhydroxide, a dimethyl polysiloxane, tetrasodium pyrophosphate, apolyethylene oxide dihydrogen or monohydrogen phosphate ester, ormixture thereof, a nonyl phenol polyethylene glycol ether andtetraethanol amine. The ingredients are dispersed in a suitable solventmedium preferably an aqueous or partially aqueous solvent medium. Thecomposition can be applied directly to the area of the equipment havinggrease and/or carbon accumulated thereon preferably While the equipmentis at a temperature above about 200 F. For example, the composition canbe applied directly to the surface of a grille heated at about 300 F. orhigher. Upon application, elfervescence occurs and normally, all orsubstantially all of the grease and carbon is rapidly removed by way ofthe effervescent action. Should the grease in some areas not be removedby the initial effervescent action, a small amount of water can beapplied dropwise to the area to re-establish the effervescent action.This operation can be continued until even the most resistantaccumulation of grease and/or carbon is completely removed from thegrille. After the effervescent action diminishes, the surface of thegrille is then rinsed thoroughly and is ready for reuse.

Many advantages of the composition of the present invention will beapparent to those skilled in the art. Chief among these is that rubbingis not normally required and the removal of the accumulated grease andcarbon from the surface is remarkably rapid. Moreover, there is anothersurprisingly unexpected advantage to be derived from the practice of thepresent invention. For example, as those skilled in the art know, foodtends to stick to freshly cleaned grilles. This is especially true withsuch food as eggs, pancakes and others which could be mentioned.However, such sticking is rarely encountered with grilles cleaned bycompositions of the present invention. This advantage is believed to bedue to the presence of the linear dimethyl polysiloxane in thecomposition.

DESCRIAPTION OF THE PREFERRED EMBODIMENT The active ingredients of thecompositions of the present invention and the percent by weight thereofwith respect to the total weight of active ingredients are set forthbelow.

Percent by weight In accordance with the practice of the presentinvention, the above described active ingredients are dissolved orotherwise dispersed in a suitable inert medium which preferably is anaqueous or partially aqueous solvent medium. For example, the amount ofwater normally employed is sufficient to provide a composition whereinwater represents from about to about 95but preferably between about toabout 88percent by weight of the combined water and active ingredients.

The invention and manners of practicing same will be better understoodby reference to the following example. It is to be understood that theexample is illustrative in nature and in no way should it be construedso as to limit the invention beyond those limitations expressly setforth in the present specification or in the claims which appearhereinafter.

EXAMPLE Mix 42.75 pounds of commercial grade NaOH (97% flake) in 900pounds of water. While stirring, slowly add 4 pounds of a 10% by weightsilicone antifoam emulsion. The silicone involved in such antifoamemulsions are linear, food grade dimethyl polysiloxanes. Additionaldetails relating to suitable silicone antifoam emulsions employed in thepresent invention can be found in Bulletin 04-096 dated February 1967and Bulletin 04-0-88 dated October 1966 both published by ChemicalProducts Division, Dow Corning Corporation, Midland, Mich. Additionaldetails relating to suitable silicone antifoam emulsons can be found onpp. 42 and 43 of Chemical and Plastics Physical Properties, 1968edition, published by Union Carbide Corporation. After mixing the aboveingredients, add 5.5 pounds of commercial grade tetrasodiumpyrophosphate (hydrate) and then add 45 pounds of Alkapent M-60.Alkapent M-60 is a mixture of polyoxyethylene mono and dihydrogenphosphate esters and specifically is a (p-nonylphenyl)omega-hydroxypoly(oxyethylene) mixture of dihydrogen phosphate andmonohydrogen phosphate esters where the poly (oxyethylene) contentaverages 6 moles. Thereafter, 30 pounds of a nonionic surface activeagent such as Tergitol NPX are added to the mixture. Tergitol N PX is anonionic, nonyl phenol polyethylene glycol ether having a hydrophilevalue (number of moles of ethylene oxide) of 10.5. Additional helpfuldetails relating to Tergitol NPX can be found on page 22 of Chemical andPlastics Physical Properties, 1968 edition, published by Union CarbideCorporation. Nonionic surface active agents having characteristics ofthe type described therein are useful in the practice of the presentinvention. For example, on page 22 there are listed five specific nonylphenol polyethylene glycol ethers wherein the hydrophobe is nonylphenoland wherein the number of moles of ethylene oxide, e.g., hydrophile,ranges from 4 in the case of NP-14 to 20 in the case of NP-40. As thefinal ingredient, add 48 pounds of commercial grade triethanol amine.The final aqueous mixture can then be packaged in squeeze bottles,aerosol cans or other suitable containers whereby the composition can beconveniently added directly to the surface of grilles, stoves or likeutensils having grease and/ or carbon accumulated thereon.

Many modifications in incidental details of the above example offeredfor the purpose of illustrating the invention can be employed withoutdeparting from the spirit and scope of the invention defined in theappended claims.

Having described the invention as well as manners of practicing same andpreferred embodiments thereof what is declared as new and desired to besecured by US. Letters iPatents as follows:

1. A cleaning composition wherein the active ingredients consistessentially of from about 10 to 40 percent by weight NaOH; from about0.05 to about 0.5 percent by weight of a linear dimethyl polysiloxane;from about 1 to about 5 percent by weight of tetrasodium pyrophosphate;from about to about 40 percent by weight of an alpha-(p-nonylphenyl)-omega-hydroxy poly-(oxyethylene) mixture of mono-hydrogen anddi-hydrogen phosphate esters wherein the oxyethylene content averages 6moles; from about 5 to about 30 percent by weight of a nonyl phenolpolyethylene glycol ether having a hydrophile value between 4 to andfrom about 10 to about 40 percent by weight of triethanol amine.

2. A cleaning composition of claim 1 wherein said ingredients aredispersed in water which is present in a concentration between about 75to about 95 percent by weight of the combined weight of water and saidactive ingredients.

3. A composition of claim 1 wherein the concentration of NaOH is fromabout 20 to about 30 percent by weight, the concentration of saiddimethyl polysiloxane is from about 0.1 to about 0.4 percent by weight.The concentration of said tetrasodium pyrophosphate is from about 2 toabout 4 percent by weight; the concentration of said alpha-(p-nonylphenyl)-omega-hydroxy poly-(oxyethylene) mixture of mono-hydrogen anddi-hydrogen phosphate esters is from about 20 to about 30 percent byweight, the concentration of said nonyl phenol polyethylene glycol etheris from about 10 to about 25 percent by weight and the concentration ofsaid triethanol amine is from about 20 to about 35 percent by weight.

4. A cleaning composition of claim 3 wherein said ingredients aredispersed in water which is present in a concentration between about toabout percent by weight of the combined weight of water and said activeingredients.

5. An aqueous cleaning composition wherein the active ingredientsconsist essentially of from about 10 to about 40 percent by weight NaOH;from about 0.05 to about 0.5 percent by weight of a linear dimethylpolysiloxane; from about 1 to about 5 percent by weight of tetrasodiumpyrophosphate; from about 10 to about 40 percent by weight of analpha-(p-nonyl phenyl)-omegahydroxy poly-(oxyethylene) mixture ofmono-hydrogen and di-hydrogen phosphate esters wherein the oxyethylenecontent averages 6 moles; from about 5 to about 30 percent by weight ofa nonyl phenol polyethylene glycol ether having a hydrophile value of10.5 and from about 10 to about 40 percent by weight of triethanolamine, said active ingredients being dispersed in water which is presentin a concentration between about 75 to about 95 percent by weight of thecombined weight of water and said active ingredients.

6. A composition of claim 5 wherein the concentration of NaOH is fromabout 20 to about 30 percent by weight; the concentration of saiddimethyl polysiloxane is from about 0.1 to about 0.4 percent by weight;the concentration of said tetrasodium pyrophosphate is from about 2 toabout 4 percent by weight; the concentration of said alpha-(p-nonylphenyl)-omega-hydroxy poly-(oxyethylene) mixture of mono-hydrogen anddi-hydrogen phosphate esters is from about 20 to about 30 percent byweight; the concentration of said nonyl phenol polyethylene glycol etheris from about 10 to about 25 percent by weight and the concentration ofsaid triethanol amine is from about 20 to about 35 percent by weight.

7. A method for cleaning a surface which comprises the step of applyingthe composition of claim 5 to said surface while said surface is heatedat a temperature above about 200 F.

8. A method for cleaning a surface which comprises the step of applyingthe composition of claim 6 to said surface while said surface is heatedat a temperature above about 200 F.

References Cited Oven cleaner digest LEON D. ROSDOL, Primary Examiner E.L. ROLLINS, Assistant Examiner US. Cl. X.R. 252-548

1. An insoluble polymeric diazonium salt chromogen having a couplingpower from 4.25 to about 350 milligrams of naphthol per gram ofchromogen as measured by Method A or Method B of the above specificationconsisting essentially of an insoluble cation exchange polymeric resinhaving reactive groups selected from the class consisting of carboxylicacid groups, potassium salts of such acid groups, and sodium salts ofsuch acid groups attached to the resin and wherein a sufficient amountof the reactive groups are each individually bonded through anacyl-amide linkage to the diazotized form of a carbocyclic aromaticdiamine moiety derived from a compound selected from the classconsisting of benzidine, o-tolidine, 0-dianisidine, phenylenediamine and2-chloro-1,4-diaminobenzene to achieve such coupling power.
 2. Achromogen according to claim 1 wherein the cation exchange resincontains carboxylic acid groups.
 3. A chromogen according to claim 1wherein the cation exchange resin contains sodium salts of carboxylicacid groups.
 4. A chromogen according to claim 1 having a couplingpower, as measured by Method A or Method B of the above specification,of from about 25 to about 45 milligrams of naphthol per gram ofchromogen.
 5. A chromogen according to claim 1 having a coupling power,as measured by Method A or Method B of the above specification, of fromabout 190 to about 350 milligrams of naphthol per gram of chromogen. 6.A process for the preparation of an insoluble polymeric diazonium saltchromogen according to claim 1 which comprises reacting An insolublecation exchange resin having reactive groups selected from the classconsisting of carboxylic acid groups, potassium salts of such acidgroups, and sodium salts of such acid groups attached to the resin witha halogenating agent to form acyl halide groups containing from 0.2 to2.37 milliequivalents of acyl halide per gram of resin, reacting theresulting acyl halide groups with a carbocyclic aromatic diamineselected from the class consisting of benzidine, o-tolidine,o-dianisidine, phenylenediamine, and 2-chloro-1,4-diaminobenzene to forma resin having a sufficient amount of the reactive groups attachedthereto each individually bonded through an acyl-amide linkage to acarbocyclic aromatic diamine moiety derived from a compound selectedfrom the class consisting of benzidine, o-tolidine, o-dianisidine,phenylenediamine, and 2-chloro-1,4-diaminobenzene, said moiety having afree amino group, to subsequently achieve a coupling power from 4.25 toabout 350 milligrams of naphthol per gram of chromogen as measured byMethod A or Method B of the above specification, and diazotizing thefree amino group of each said moiety to produce the insoluble polymericdiazonium salt chromogen having the above coupling power.